Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C327/00—Thiocarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
  • C08K5/38—Thiocarbonic acids; Derivatives thereof, e.g. xanthates ; i.e. compounds containing -X-C(=X)- groups, X being oxygen or sulfur, at least one X being sulfur
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
  • C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
  • C09K15/12—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing sulfur and oxygen
  • C09K15/14—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing sulfur and oxygen containing a phenol or quinone moiety
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
  • C10M135/12—Thio-acids; Thiocyanates; Derivatives thereof

Definitions

• the present invention relates to new S- (4-hydroxyphenyl) thioester derivatives, their use as stabilizers and the organic material stabilized therewith.
• Organic polymeric compounds such as plastics or resins are subject to thermal, oxidative or light-induced degradation.
• a large number of stabilizers for a large number of substrates are known in the art.
• the effectiveness of a stabilizer depends, among other things, on the type of substrate in which it is used and on the particular degradation mechanism. It is therefore generally difficult to specify the most effective and economical stabilizer for a specific application.
• a stabilizer that reduces the volatility of a compound can act to prevent the substrate molecules from breaking the bond.
• a stabilizer can be required to prevent excessive crosslinking reactions and / or chain breakage.
• it In order to prevent yellowing of a substrate, it must be prevented that reactions of the substrate or the stabilizer take place, which lead to new chromophores.
• problems of processing stability and substrate compatibility have to be considered.
• the compounds according to the invention prove to be particularly useful stabilizers for polyolefins, impact-resistant polystyrene, elastomers such as polybutadiene or styrene-butadiene elastomers or other elastomers in which the preservation of elasticity, the prevention of crosslinking reactions from discoloration, odor formation and exudation of the stabilizer are fundamental Represent requirements for the quality of a stabilizer.
• Thioesters are described in JP-Kokai 67, 6 332 and in JP-Kokai 74, 116 036 as antioxidants.
• the present invention relates to compounds of the formula I. wherein R and R 1 are independently hydrogen, C 1 -C 12 alkyl, C 5 -C 6 cycloalkyl, phenyl, substituted by C l -C 12 -alkyl-substituted phenyl, C 7 -C 9 aralkyl or C 1 -C 12 alkyl substituted C 7 -C 9 aralkyl, and in which AC 1 -C 10 alkylene, C 5 -C 6 cycloalkylene, arylene, biphenylene or hydroxy-substituted arylene.
• the radicals R and R 1 are preferably straight-chain or branched C 1 -C 8 alkyl, such as, for example, methyl, n-butyl, sec-butyl, tert-butyl, tert-pentyl, 2-ethylhexyl, n-octyl or 1 , 1,3,3-tetramethylbutyl.
• the radicals methyl, tert-butyl, tert-pentyl and 1.1.3.3-tetramethylbutyl are particularly preferred.
• R or R 1 is cyclopentyl or cyclohexyl, preferably cyclohexyl.
• R and R 1 as aralkyl mean, for example, benzyl, a-methylbenzyl or a, a-dimethylbenzyl.
• R and R 1 mean, for example, tolyl, mesityl or xylyl.
• A means, for example, methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene or decamethylene.
• arylene A is preferably o-, m- or p-phenylene.
• Preferred compounds of the formula I are those in which AC 1 -C 10 alkylene, preferably C 4 -C s alkylene, and particularly preferably C 8 alkylene, or in which A is phenylene, and in which R and R 1 are tert-butyl are.
• the compounds according to the invention can be prepared by reacting a suitable mercaptophenol with a carboxylic acid chloride in the presence of a proton acceptor.
• Typical proton acceptors are, for example, lithium salts, tertiary amines, alkali metals. Alkali metal and alkaline earth metal hydroxides, carbonates, and the like.
• the reaction is carried out in solution.
• suitable solvents are aromatic hydrocarbons, such as benzene, toluene, xylene or the like, or aliphatic hydrocarbons, such as heptane.
• the reaction is carried out in the temperature range from 0 to 70 ° C.
• the starting materials for the preparation of the compounds according to the invention are commercially available or can be prepared by known processes.
• the compounds according to the invention can be used as stabilizers for organic material such as plastics, elastomers or resins; They can also be used as stabilizers for mineral oils or synthetic oils, for example for lubricants or heat exchange oils.
• the invention therefore also relates to a composition
• a composition comprising an organic material which is sensitive to oxidative, thermal or radiation-induced degradation and at least one compound of the formula I as a stabilizer, organic material preferably being understood as a polymer or a lubricating oil, but particularly preferably a polyolefinic homo- or copolymer, but in particular also a homopolymer, copolymer or terpolymer of styrene, or a lubricating oil which is derived from the mineral oil.
• the compounds of the formula I can be used in particular to stabilize the homopolymers or copolymers of polyolefins.
• the following polyolefinic substrates can preferably be stabilized with the substances according to the invention: polyethylene, polypropylene, polyisobutylene, poly (butene-1), poly (pentene-1), poly-3 (methylbutene-1), poly (4-methylpentene) 1), different ethylene-propylene copolymers, EPM, EPDM and similar compounds, polystyrene and its copolymers or terpolymers, such as impact-resistant polystyrene, ABS resins, SBR, polyisoprene, polybutadiene, nitile rubber, natural rubber, or polyesters such as polyethylene terephthalate, Polybutylene terephthalate and its copolymers.
• polyurethanes, polycarbonates or polyamides such as nylon 6, nylon 6/6 or the like, and their copolymers or polysulfones can be stabilized with the compounds according to the invention.
• compositions wherein the organic material is a synthetic lubricant or a mineral oil based lubricant.
• lubricants in question are familiar to the expert and z. B. in the «lubricant paperback (Hüthig Verlag, Heidelberg, 1974) described.
• the invention further relates to a method for stabilizing organic material against oxidative, thermal or radiation-induced degradation, characterized in that at least one compound of the formula I is added to the material as described above.
• Another object of the invention is the use of compounds of formula I as stabilizers for organic material against damage by the action of oxygen, heat, light and high-energy radiation.
• the stabilizers according to the invention are mixed into the plastics in amounts of 0.01 to 5% by weight, based on the stabilized material.
• the amount of stabilizer is varied depending on the use and substrate. It is preferred to use 0.05 to 2% by weight of the stabilizer, particularly preferably 0.1 to 1% by weight.
• the incorporation can be carried out, for example, by mixing in the substances of the formula and, if appropriate, further additives using the methods customary in industry, before or during shaping, or else by applying the dissolved or dispersed compounds to the polymer, optionally with subsequent evaporation of the solvent.
• the new compounds can also be added to the plastics to be stabilized in the form of a masterbatch which contains these compounds, for example in a concentration of 2.5 to 25% by weight.
• the compounds are added before cross-linking.
• the materials stabilized in this way can be used in various forms, e.g. B. as films, fibers, tapes, molding compounds, profiles or as binders for paints, adhesives or putties.
• Lubricant formulations can additionally contain other additives that are added to improve certain performance properties, such as. B. further aminic antioxidants, metal passivators, rust inhibitors, viscosity index improvers, pour point depressants, dispersing agents / surfactants and wear protection additives.
• a solution of 3.84 g (0.021 mol) of adipoyl chloride, 50 ml of toluene and 50 ml of heptane is prepared in a flame-dried flask under nitrogen. The solution is cooled in an ice bath. A solution of 10.0 g (0.042 mol) of 2,6-di-tert-butyt-4-mercaptophenol, 4.25 g (0.042 mol) of triethylamine in 50 ml of toluene and 50 ml of heptane is then added dropwise. After the addition has ended, the suspension obtained is allowed to warm to room temperature and stirred until the mercaptan originally used has reacted (determined by thin layer chromatography).
• Example 2 The procedure described in Example 1 is repeated using 5.02 g (0.021 mol) of sebacoyl chloride, 10.0 g (0.042 mol) of 2,6-di-tert-butyl-4-mercaptophenol and 4.25 g (0.042 Mol) triethylamine in 100 ml of toluene and 100 ml of heptane reacted with each other. After recrystallization from acetonitrile, 6.2 g (yield 46%) of a white powder of FP 82 ° C.-85 ° C. are obtained.
• Example 2 The procedure described in Example 1 is repeated using 4.26 g (0.021 mol) of terephthalalo yl chloride, 10.0 g (0.042 mol) of 2,6-di-tert-butyl-4-mercaptophenol and 4.25 g (0.042 mol) of triethylamine in 400 ml of toluene. After recrystallization of the residue from methyl ethyl ketone, 10.0 g (yield 78%) of white crystals of FP 310 ° C.
• table 1a shows the results of the ductility measurements and the measurements of the yellowness index of samples aged at 80 ° C.
• table 1 b contains results of samples aged at 150 ° C.
• Unstabilized polypropylene powder (Hercules Profax® 6501) is mixed with 0.2% by weight of an additive. These mixtures are then plasticized at 182 ° C for 5 minutes on a mixing mill. The stabilized polypropylene film is then removed from the rolling mill and allowed to cool. The film is cut into pieces and shaped into a 0.13 mm thick sample on a hydraulic press at 220 ° C. and 12 bar. This sample is exposed to ultraviolet light until it decomposes. The number of hours at which the first signs of disintegration (cracks, brown corners) appear is the time of decomposition. The measurement data are shown in Table 2 below.
• Unstabilized polypropylene powder (Hercules Profax @ 6501) is mixed with 0.2% by weight of the respective stabilizer.
• polypropylene samples are produced which contain 0.1% by weight of a compound according to the invention and 0.3% by weight of distearyl- ⁇ -thiodipropionate (DSTDP).
• DSTDP distearyl- ⁇ -thiodipropionate
• the samples pretreated in this way are comminuted and then shaped for 5 minutes in a hydraulic press at 220 ° C. and under a pressure of 12 bar to give plates of a thickness of 0.64 mm. These plates are aged at 150 ° C in a forced air oven. The number of hours after which the samples show the first external signs of decay (brown corners, cracks) is taken as the time of decomposition.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Engineering & Computer Science (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Health & Medical Sciences (AREA)
• Materials Engineering (AREA)
• General Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Anti-Oxidant Or Stabilizer Compositions (AREA)

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• 1983
  • 1983-07-29 US US06/518,561 patent/US4508865A/en not_active Expired - Fee Related
• 1984
  • 1984-07-23 EP EP84810361A patent/EP0134194B1/de not_active Expired
  • 1984-07-23 DE DE8484810361T patent/DE3460701D1/de not_active Expired
  • 1984-07-27 CA CA000459928A patent/CA1233478A/en not_active Expired
  • 1984-07-30 JP JP59160200A patent/JPS6056952A/ja active Pending

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